A series of ferrocene modified hyperbranched polyethers HBPO-Fe with different ferrocene content were obtained by cation ring-opening polymerization followed by esterification. Electrochemical behaviors HBPO-Fe were investigated by cyclic voltammetry (CV) and the influence of ferrocene content of HBPO-Fe, scan rate, solvent and electrolyte concentration oil the electrochemical behaviors of HBPO-Fe were discussed, and the dynamic parameters in electrode processes were calculated. Anion recognition of HBPO-Fe was studied by CV and UV-vis. The binding capacities of HBPO-Fe to different anions were compared, and the binding capacities of HBPO-Fe with different ferrocene content were also discussed. Finally, binding models of HBPO-Fe to anions were proposed.